|Publication number||US8129190 B2|
|Application number||US 11/561,119|
|Publication date||Mar 6, 2012|
|Filing date||Nov 17, 2006|
|Priority date||Nov 17, 2006|
|Also published as||CA2670410A1, CA2670410C, CN101606069A, CN101606069B, EP2095131A1, EP2095131A4, US20080118982, WO2008063942A1|
|Publication number||11561119, 561119, US 8129190 B2, US 8129190B2, US-B2-8129190, US8129190 B2, US8129190B2|
|Inventors||Philip Forshee, Peter Kottenstette|
|Original Assignee||Applied Nanotech Holdings, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (28), Non-Patent Citations (3), Classifications (12), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This invention relates to tagged petroleum products, and also to methods of detecting the same.
For a myriad of reasons, attempts are often made to copy or imitate products for commercial gain. While counterfeit products will often appear visually identical to the original products, the counterfeit products often will not authentically posses the properties that impart the favorable attributes of the original. Such deception can cause harm, sometimes irreparable harm, such as to the brand name or brand image of the producer of the original product. Significant commercial gain can also be obtained by counterfeiters through the dilution of the original products with a readily available, less expensive material.
For instance, petroleum products can be tagged for identification purposes with coloring agents to provide a distinct color visually perceptible to the naked eye. Such tagging allows these tagged petroleum products to be distinguished from other petroleum products for a number of reasons, including to distinguish the manufacturer, to differentiate similar fuels taxed at different rates, to identify various grades of the fuels, to render untraceable the adulteration, counterfeiting, and/or misuse of the petroleum product, and to make it hard to detect other unlawful practices (such as tax evasion and theft).
For lower taxed petroleum products, governments have commonly required these to be colored so that they may be distinguished from similar fuels subject to higher tax rates and to assist in the detection of tax evasion. Petroleum products are also colored by oil companies that market brand name products (such as gasoline) to prevent misuse by their dealers. Such oil companies must insure that their branded products meet specifications regarding volatility and octane specifications, and they also provide their products with effective packages containing detergents and other additives. To do so, there is a price the oil companies must pay. In turn, consumers recognize the value of these name brand products and are willing to purchase the petroleum products at a higher price due to the increase quality. By imitating or diluting the branded product, a dealer can take advantage of consumers and reap increase profits while selling an inferior product.
It is also known that coloring agents are not always reliable. The coloring agent may be removed by relatively simple methods such as acid/base reactions. Or natural substances or the additives may obscure the coloring agents and make them difficult to detect. Another problem a high dosage level of the coloring agent is need for detection, which can create increased costs and other problems.
What is needed is a tagging compound that can be added to an original product to provide for a more secure technique for the field determination of authenticity of the product. The tagging compound should not be easily removable. Also, it would be beneficial if little training of the monitoring personnel is required and the tagging compound used for marking or tagging the original product was relatively inexpensive.
This invention relates to tagged petroleum products, and also to methods of detecting the same. For example, the tagged petroleum product can be tagged with a violanthrone (e.g., a substituted violanthrone) or an isoviolanthrone (e.g., a substituted isoviolanthrone).
In one aspect, the invention features tagged products that include a petroleum product and a tagging compound of Structure I and/or Structure II, as shown in
In some embodiments of the invention, to enable their detection, a concentration of at least about 1 ppb by weight of the tagging compound is dissolved in the petroleum product.
In some embodiments, at least one R (Rz) is a moiety that includes between 1 and 36 carbon atoms, inclusive. In such embodiments, Rz can further include at least one N, O, S, F, Cl, Br, or I atom.
In some embodiments at least one R (Rz) is a moiety that includes between 1 and 36 carbon atoms, inclusive. In some particular embodiments, Rz includes only carbon and hydrogen atoms. For example, Rz can be C1-C21 alkyl, C1-C8 cylcoaklyl, C1-C21 alkenyl, C1-C10 aryl or C1-C21 alkylaryl.
In some other embodiments, at least one R (Rz) is a moiety that includes between 1 and 36 carbon atoms, inclusive. In some particular embodiments, the moiety only includes carbon, hydrogen and oxygen. For example, the moiety that includes only carbon hydrogen and oxygen can include an ether or an ester group, e.g., one that is attached directly to the core structure.
In some instances, the tagging compound is of Structure III, as shown in
In some implementations, the tagging compound is of Structure IV, as shown in
In some other implementations, the tagging compound is of Structure V, as shown in
In some embodiments, at least one R (R2) is a moiety that includes between 1 and 36 carbon atoms, inclusive. In such embodiments, the moiety can define a ring, e.g., one, two, three or four rings. For example, the rings can be 5-6, or 7-membered rings. For example, the ring can be carbocyclic or heterocyclic.
Examples of petroleum products include gasoline, kerosene, diesel, naphtha, lubricant oil, furnace oil, or mixtures of any of these, e.g., mixtures of gasoline and kerosene, which is more commonly known as military jet fuel or JP4.
In some embodiments, the concentration of the tagging compound in the tagged product is between about 0.001 ppm and about 1000 ppm on a weight basis. Low concentrations are desirable for cost and product integrity and/or performance reasons.
In other embodiments, the tagging compound responds to near infrared light. For example, the tagging compound can absorb and/or emit near infrared light.
In another aspect, the invention features methods that include selecting a sample of a tagged product in which the tagged product includes a petroleum product and a tagging compound of Structure I and/or Structure II; and detecting the tagging compound in the tagged product.
In some embodiments, the tagging compound is dissolved in the product at a concentration of at least about 1 ppb by weight. This can allow for the tagging compound to be easily detected.
For example, the detecting step can include detecting a response of the tagging compound. For instance, the response can be (i) emissions from the tagging compound, (ii) absorbances by the tagging compound or (iii) emissions from a reaction product formed by reacting the tagging compound with another compound.
In some embodiments, the response includes an emission from and/or an absorbance by the tagging compound. For example, emission and/or absorbance can occur at a wavelength between about 500 nm and about 900 nm.
Although sometimes just detecting the presence of the tagging compound is desired, in other embodiments, it is advantageous to quantitate the response.
In another aspect, the invention features a tagged product that includes a petroleum product and a first tagging compound dissolved in the petroleum product. The first tagging compound can be a non-substituted violanthrone, a substituted violanthrone, a non-substituted isoviolanthrone, a substituted isoviolanthrone or combinations thereof.
In some embodiments, the first tagging compound has a solubility of greater than about 0.5 percent by weight in toluene, e.g., greater that 1 percent by weight in toluene. High solubility can be desirable because concentrates of the violanthrone or isoviolanthrone can be produced. Concentrates make it easy to add a small amount of the tagging compound to a larger volume of a petroleum product, e.g., during online blending of gasoline or jet fuel.
In some embodiments, the first tagging compound is substituted with at least one moiety that comprises between 1 and 36 carbon atoms, inclusive.
In some implementations, the tagged product further includes a second tagging compound dissolved in the petroleum product along with the first tagging compound. In such implementations, the second tagging compound, which is different from the first tagging compound, is a non-substituted violanthrone, a substituted violanthrone, a non-substituted isoviolanthrone, a substituted isoviolanthrone or combinations thereof.
In some embodiments, the second tagging compound has a solubility of greater than about 0.5 percent by weight in toluene, e.g., greater than 1 percent by weight in toluene.
For detection, it is desirable that the first tagging compound be dissolved in the petroleum product at a concentration of at least about 1 ppb by weight, and that the second tagging compound also be dissolved in the petroleum product at a concentration of at least about 1 ppb by weight.
In another aspect, the invention features methods that include selecting a sample of a tagged product that includes a petroleum product; collecting absorbance and/or emission data on the tagged product; and comparing the collected data to data for tagging compounds to identify a source of the tagged product. The data for tagging compounds is data for compounds of Structure I and/or Structure II. For example, the data collected on the sample can be compared to a library having wavelength data and concentration versus absorbance data for compounds of Structure I and/or Structure II.
Embodiments and/or aspects can have any one of, or combinations of, the following advantages. The tagging compounds are combustible. The tagging compounds do not significantly reduce the performance of the petroleum products to which they are added to, nor do they appreciably change the physical and/or chemical properties of the petroleum products with which they are added to. The tagging compounds are detectible in the tagged petroleum product at a low concentration, e.g., above 1 ppb by weight, e.g., from about 0.001 ppm by weight to about 1000 ppm by weight. The compounds are readily soluble in petroleum products, e.g., aromatic petroleum products, such as benzene, toluene, a xylene, a mesitylene, Aromatic 100 (C9-C10 aromatic mixture). Aromatic 150 (C10-C11 aromatic mixture) or Aromatic 200 (C10-C14 aromatic mixture). High solubility can allow for the preparation of concentrates, which are a convenient form to add to a petroleum product. For example, the tagging compounds can have a solubility greater than 0.25 weight percent in the petroleum product, e.g., greater than 0.5 percent, greater that 1 percent, 1.5 percent, 2.0 percent, or even greater than 5 percent by weight in the petroleum product.
Furthermore, the tagging compounds are chemically stable, e.g., not prone to oxidation, degradation and/or thermal rearrangements. The tagging compounds do not tend to crystallize and/or agglomerate in a petroleum product. The tagging compounds can be detected and their concentration quantitated using commercially available fluorometers or infrared spectrometers, e.g., near infrared spectrometers. Mixtures of the tagging compounds can be used to make counterfeiting even more difficult because the ratios of the compounds can be predetermined, resulting in a unique “spectral fingerprint.” The tagging compounds are relatively inexpensive to prepare.
Optionally, the tagging compounds can be detected by measuring chemiluminescence generated from a reaction product of the tagging compound and a reactant, such as a strong oxidizing agent, e.g., an organic peroxyoxalates, optionally in combination with a peroxide. Many of the tagging compounds absorb and/or emit in the near infrared region of the spectrum, e.g., between about 650 nm and about 900 nm, but have little or no absorbance in the visible region of the spectrum, e.g., from about 400 nm to about 650 nm, making the tagging compounds “invisible” to the naked eye. As a result, the tagging compounds do not appreciably change the color of petroleum product to which they are added.
As used herein, “petroleum products” are hydrocarbon compounds or mixtures derived from processing natural gas or petroleum. This processing typically occurs at oil refineries, gas processing plants, and gasoline plants. Petroleum products include, e.g., butane, propane, benzene, toluene, gasoline, heating oil, aviation fuel, kerosine and diesel fuel. Also included are hydrocarbon feedstocks, such as ethylene and propylene. Intermediate and finished products manufactured at petrochemical plants by further processing hydrocarbon feedstocks, e.g., by the addition of chlorine, nitrogen, or oxygen to the hydrocarbon feedstocks are not considered to be petroleum products. For example, ethylene glycol, which is used in car antifreeze is not considered a petroleum product.
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety for all that they contain.
Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
Violanthrones (e.g., substituted violanthrones), isoviolanthrones (e.g., substituted isoviolanthrones) or combinations thereof are typically near infrared fluorophores that are highly effective tagging compounds for the identification of petroleum products. Generally, the violanthrone and isoviolanthrone tagging compounds have adequate thermal stability, and little light absorption in the visible region of the spectrum. As such, the tagging compounds impart little or no color to the petroleum product to which they mixed. Advantageously, the tagging compounds also have a strong absorption and/or emission in the near infrared region of the spectrum (e.g., wavelengths of about 670 nm-2500 nm), allowing for their easy detection.
Referring now to
Generally, a tagged product includes a petroleum product, and one or more violanthrone and/or isoviolanthrone tagging compounds. Referring now to
In some embodiments, the tagged product has a concentration of at least about 1 ppb by weight of the tagging compound dissolved in the petroleum product. For example, the concentration can be greater than about 2, 3, 10, 25, 50, 75, 100, or greater than about 250 ppb by weight. For example, for cost reasons and for reducing the likelihood that the tagging compound will reduce the performance of the petroleum product, the concentration of the tagging compound in a finished petroleum product is advantageously less than about 2500 ppb by weight, e.g., less than 2000 ppb, 1500 ppb, or less than 1000 ppb by weight.
In some embodiments, n is between 1 and 6, e.g., between 2 and 5.
In some instances, at least one R (Rz) is a moiety that includes between 1 and 36 carbon atoms, inclusive. In such instances, the one or more moieties that include between 1 and 36 carbon atoms can further include one or more N, O, S, F, Cl, Br, or I atoms. For example, each R can be moiety that includes between 1 and 36 carbon atoms and includes only carbon, hydrogen and oxygen atoms. For example, each R can include one or more ester or ether groups. For example, the ester or ether group can be bonded directly to the violanthrone or isoviolanthrone core or it can be along R.
In some embodiments, at least one R (Rz) is a moiety that comprises between 1 and 36 carbon atoms, inclusive, and includes only carbon and hydrogen atoms (i.e. is a hydrocarbon fragment). For example, the hydrocarbon fragment can be a C1-C21 alkyl, a C1-C8 cylcoalkyl, a C1-C21 alkenyl, a C1-C10 aryl, or a C1-C21 alkylaryl.
In some embodiments, at least one R (Rz) is a moiety that includes between 1 and 36 carbon atoms, and at least some of the carbon atoms define one or more ring systems. For example, the defined rings can be, e.g., 3-, 4-, 5-, 6-, 7-, 8-, or 9-membered rings. For example, the defined rings can be carbocylic or hetrocyclic.
Referring now to
Referring now to
Examples of petroleum products to which the tagging compounds can be added include gasoline, kerosene, diesel, naphtha, lubricant oil, benzene concentrate, butadiene monomer, isooctane, furnace oil, propylene monomer, liquefied petroleum gas, petroleum waxes and mineral oil.
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Generally any of the tagging compounds described herein absorb and/or emit in the near infrared region of the spectrum, e.g., between about 600 nm and about 1000 nm, between about 650 nm and 950 nm or between about 700 nm and 900 nm.
As an overview, to detect a tagging compound in a tagged product, a tagged petroleum product having any one or more of the violanthrones and/or isoviolanthrones described herein is selected, and then the tagging compound is detected. For detection, generally the concentration of the tagging compound in the petroleum product should be at least about 1 ppb by weight.
The tagging compound can be detected by a response of the tagging compound. For example, the response can be emissions from the tagging compound, absorbances by the tagging compound, or even emissions from a reaction product formed by reacting the tagging compound with another compound.
In some embodiments, the emission and/or the absorbance is quantified to determine the concentration of the tagging compound or compounds. For example, the absorbance can be quantified by integration of the detected signal, and then comparing the integrated signal to a calibration curve. In some embodiments, a full spectrum is obtained of the tagging compound or compounds to obtain a fingerprint of the tagging compound or compounds. In some embodiments, at least two tagging compounds are utilized and a ratio of their emission and/or absorbance is used to determine authenticity of a sample.
In some embodiments, emission and/or absorbance data is collected on the tagging compound or compounds, and then the data collected is compared to data for a library of tagging compounds to identify a source of the tagged product.
In some embodiments, the response includes a chemiluminescent emission from a reaction product generated by a reaction of the tagging compound with another compound, such as an oxidizing agent, e.g., a peroxide and/or an oxalate. For example, in one embodiment, chemiluminescence is generated by mixing the tagged petroleum product with an oxalate, e.g., bis(6-carbopentoxy-2,4,5-trichlorophenyl) oxalate, and a peroxide material, e.g., hydrogen peroxide in combination with sodium salicylate. Chemiluminescent systems are described by Vega, U.S. Pat. No. 4,076,645, issued Feb. 28, 1978, to Vega: U.S. Pat. No. 4,313,843, issued Feb. 2, 1982, to Bollyky et al., and, U.S. Pat. No. 4,678,608, issued Jul. 7, 1987, to Dugliss.
The disclosure is further described in the following example, which does not limit its scope.
Preparation of the 16,17-di-2-ethylhexyl ether (7) of 16,17-di-hydroxy violanthrone (2). Referring to
After the 20 hour reaction period, 300 mL of water was added to the contents of the flask, which was acidified using several drops of concentrated sulfuric acid. After acidification, the solution was clear with a fine, dark participate suspended therein. The dark precipitate was captured on a glass frit, to produce a dark, solid cake of material.
To remove traces of the starting diol (2), the solid cake was treated with chloroform to re-solubilize the desired product (7) (diol (2) being insoluble in chloroform), and then the chloroform extract was dried over magnesium sulfate. The magnesium sulfate was filtered away and the solvent was removed with a rotary evaporator. A small amount of liquid remained after removal of the chloroform (likely DMF and/or 2-ethylhexyl bromide), which was removed under high vacuum, giving 1.28 mmol (0.910 g, 60 percent yield) of a dark blue, crystalline solid of the desired compound (7) (FW=712.91 g/mol).
The purified compound (7) above can be added to a petroleum prouct for tagging, or a concentrate of the purified product can be produced, which can latter be added to a petroleum product for tagging.
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
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|3||Letter from Foreign Associate enclosing patent certificate, mailed Dec. 2, 2009, 1 page.|
|U.S. Classification||436/56, 436/139, 208/15|
|Cooperative Classification||G01N33/2882, Y10T436/13, C10L1/003, Y10T436/21, C10L1/1857|
|European Classification||C10L1/00C, C10L1/185C, G01N33/28G8|
|Apr 24, 2007||AS||Assignment|
Owner name: AUTHENTIX, INC., TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FORSHEE, PHILIP;KOTTENSTETTE, PETER;REEL/FRAME:019205/0035;SIGNING DATES FROM 20070313 TO 20070314
Owner name: AUTHENTIX, INC., TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FORSHEE, PHILIP;KOTTENSTETTE, PETER;SIGNING DATES FROM 20070313 TO 20070314;REEL/FRAME:019205/0035
|Apr 18, 2008||AS||Assignment|
Owner name: SILICON VALLEY BANK, AS ADMINISTRATIVE AGENT, TEXA
Free format text: SECURITY AGREEMENT;ASSIGNOR:AUTHENTIX, INC.;REEL/FRAME:020817/0742
Effective date: 20080418
|Jul 31, 2012||CC||Certificate of correction|
|Sep 2, 2015||FPAY||Fee payment|
Year of fee payment: 4